The Chemistry of Thioether-Substituted Hydroquinones and Quinones. I. The 1,4-Addition of a Heterocyclic Mercaptan to Quinones

Abstract

Fraction 7 was successfully crystallized in the collection tube, leading to one crop of crystals, m.p. 90-93.5°, easily shown to be identical with an authentic sample of 2,3,4-trimethylquinoline, lit.6 m.p. 90-92°, by the identity of their infrared spectra. A second crop, m.p. 67-75°, isolated in very small yield, was shown by mass spectra (parent peak at mass 171 ± 4) and ultraviolet spectra (long wave-length maxima at 320, 314, and 307 mg) to be a trimethylquinoline. The infrared spectrum showed that substitution had occurred in the benzene ring (absorption at 775 and 820 cm.-1) and in fact the spectrum proved to be identical with that of an authentic sample of 2,4,5-trimethyIquinoline.16 "Butanone Anil" 2,4-Diethyl-2-methyl-l,2-dihydroquinoline. -Aniline and 2-butanone reacted according to the procedure given by Vaughan4 for the preparation of 2,2,4-trimethyl-l,2dihydroquinoline. 2-Butanone (835 g.) was passed into the reaction mixture of aniline (279 g.) and iodine, (9 g.), which was maintained at 170-175°. The product was crudely distilled to separate butanone and the bulk of the aniline, then fractionated on a 4-ft. glass helix column and the fraction, b.p. 170-174°( 28 mm.), 95 g. (lit.18 b.p. 152-153°at 12 mm.), collected. The n.m.r.showed a vinyl resonance at 4.95 , the NH resonance at 6.73 , and a quartet centered at 7.55 t(J = 7.5 c.p.s.), assigned to the methylene group at position 4 of XII.The remainder of the spectrum consisted of the usual aromatic multiplet, a single resonance at 8.82 assigned to the methylene group at C-2 of XII, and a pattern of seven lines interpreted as a triplet centered at 8.87t ( J = 7.5 c.p.s.) overlapped on the low field side by a quartet centered at 8.69 (J = 7.5 c.p.s.) and on the high field side by a triplet centered at 9.13 (/ = 7.5 c.p.s.). The seven line pattern thus represents the two methyl groups attached to methylenes at C-2 and C-4, and the methylene attached to the saturated center at C-2.A sample purified by v.p.c. gave the following analysis.

Tandem phenol‐keto tautomerism and nucleophilic substitution reactions for the synthesis of novel soluble and crosslinkable poly(arylene ether ketone)

“…The success may be explained by the route shown in Scheme (b), where the intermediate 1, 4‐dihydro‐1,4‐methanonaphthalin‐5, 8‐diol ( 2 ) were first gained through phenol‐keto tautomerism and then the 2 formed in situ immediately react with corresponding DFK by nucleophilic substitution reactions to yield expected PAEK‐ 1, PAEK‐ 2, and PAEK‐ 3, respectively. It is well known that compound 1 can be rearranged to aromatic compound 2 via prototropic tautomerism involving the relocation of an H atom and a double bond in the presence of base, 7, 8 that is phenol‐keto tautomerism, where deprotonated intermediate in the interconversion referred to as an phenolate anion is a good nucleophile. Evidentially, the literature was reported that compound 1 could react with alkyl halide to afford ether compound in the presence of K 2 CO 3 in one‐pot.…”

“…In this article, we report a successful synthetic method of the novel amorphous PAEKs with norbronylene ring group via one‐pot tandem phenol‐keto tautomerism and nucleophilic substitution reactions. One feature of this work avoid the diphenol derivatives synthesis while using its precursor, tricyclo[6.2.1.0 2, 7]undeca‐4,9‐diene‐3,6‐dione ( 1 ). The other is that the resultant PAEKs could occur the crosslinking reaction through a plausible retro‐Diels–Alder reaction at elevated temperature, combining the processing advantages found in the amorphous PAEK and high‐performance properties of their semicrystalline analogs.…”

Reaction of Thiols With Epoxides of Conjugated 1,4-Diketones

“…[3]. The reduction of the isolated double bond appears to have decreased the strain on the bicyclic ring system, for the enedione S L V readily rearranged after the addition of a trace of mineral acid or after a long reflux period ; the correspoilding unsaturated eilediones of X I X , XX\III, and X S X I required a base for rearrangement (4,5). r: D a n ; r;…”

The Chemistry of the Aminochromes: Part Vi. The Reaction of Adrenochrome With Glutathione

“…Most of the previously reported additions of this type involved p-quinones; however, there have been a number of examples of the reported addition of thiols, including glutathione, t o oxidized catechol derivatives (cf. [7][8][9][10][11] and recently the I$-addition of a thiol (l-phenyl-5-mercaptotetrazole) t o several quinones, including some o-quinones, has been described (12,13).…”